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Fluorescence Quenching in Electron-Donating Solvents. 2. Solvent Dependence and Product Dynamics

Contributors

Morandeira, Ana; Fürstenberg, Alexandre; Vauthey, Eric

Published in

The journal of physical chemistry. A, vol. 108, no. 40, p. 8190-8200

Publication date

2004

Abstract

The electron transfer quenching dynamics of excited perylene and cyanoperylene in various donating solvents has been investigated by using ultrafast fluorescence up-conversion and multiplex transient grating. The strongly nonexponential fluorescence decays have been analyzed by using the orientational model described in the first article of this series (J. Phys. Chem. A 2003, 107, 5375). It appears that the solvent dependence of the quenching dynamics is strongly connected to the number of surrounding donor molecules enabling ultrafast electron transfer. This number depends mainly on the driving force for electron transfer, on steric interactions, and on the occurrence of dipole−dipole interactions with the acceptor. The quenching product is an exciplex with a strong charge-transfer character. The complicated wavelength dependence of the fluorescence dynamics in the exciplex region, as well as the spectral dynamics observed in the transient grating data, is attributed to dipolar solvation, which leads to an increase of the charge-transfer character of the exciplex. The strong donor dependence of the exciplex lifetime is very similar to that reported earlier for the charge recombination time of geminate ion pairs in acetonitrile, and can be rationalized in terms of different intramolecular reorganization energies and electronic coupling constants.

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UNIGE research groups

Citation (ISO format)

MORANDEIRA, Ana, FÜRSTENBERG, Alexandre, VAUTHEY, Eric. Fluorescence Quenching in Electron-Donating Solvents. 2. Solvent Dependence and Product Dynamics. In: The journal of physical chemistry. A, 2004, vol. 108, n° 40, p. 8190–8200. doi: 10.1021/jp048048c

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Article (Published version)

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Additional URL for this publication

http://pubs.acs.org/cgi-bin/article.cgi/jpcafh/2004/108/i40/pdf/jp048048c.pdf

Journal ISSN

1089-5639
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Technical informations

Creation

02/10/2009 15:19:30

First validation

02/10/2009 15:19:30

Update

14/03/2023 15:15:52

Status update

14/03/2023 15:15:52

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